Manbfactobe of condensation



Patented Get. 15, 1940 ETED STATES PATENT mu MANUFACTURE OF CONDENSATKONPRODUCTS FROM PHENOLS No Drawing' Application December 27, 1938, Se-

rial No. 247,944. In Great Britain January 3,

This invention relates to'the manufacture of condensation products fromsubstituted phenols.

More particularly it relates to the conversion of substituted phenolsinto new water-solublecompounds which are useful as assistants in thedyeing of cellulose fabrics and are believed to be quaternary ammoniumsalts.

It is known to obtain water-soluble products, believed to be quaternaryammonium compounds, by causing an aqueous formaldehyde solutionsaturated with gaseous hydrogen halide to react with a phenol or a,homologue of a phenol, the so obtained halogenomethyl phenols beingsubsequently reacted with pyridine.

It is also known to obtain quaternary ammonium compounds by causing anaqueous solution of formaldehyde saturated with hydrogen chloride toreactwith a phenol containing one orv more aliphatic carbon chains,which contain at leastc carbon atoms, the so obtained reaction productbeing subsequently treated with a tertimy base, such as for example,pyridine or quincline. 7

These processes suffer from the disadvantage that phenol formaldehyderesins are apt to form during the reaction. Furthermore, it does notseem possible by this procedure to introduce more than onehalogen-methyl group into each phenol radical. The resulting quaternarycom-.

pound, therefore, cannot have more than one methylene-ammonium radicalper phenol radical. This invention has as an object to devise a newmethod of manufacturing condensation products from substituted phenolswhich will be useful as assistants in the dyeing of cellulose We havenow found that water-soluble compounds, which are believed to bequaternary am monium salts, are obtained by a process which comprisesreacting a substituted phenol, as hereinaiter defined, with a salt of aheterocyclic tertiary amine for example, pyridine, a C-alkylpyridine orquinoline, and/or with an addition compound of the said heterocyclictertiary amine and an inorganic acid anhydride.

' hydrochloride.

9 Claims. (Cl. 280-288) According to the invention we cause to interacta salt and/or an inorganic acid anhydride addition compound of aheterooyclic tertiary amine (for example, pyridine, a C-alkylpyridine,or quinoline) and a phenol which is substituted by one or morehydroxymethyl groups and which may be Iurther substituted, either inthe-nucleus or in a side chain, by' one or more of the following atomsor groups, namely halogen atoms, acylamido, acylamldomethyl, alkyl,aralkyl or hydroxyaralkyl groups (which last mentioned groups themselvesmay carry hydroxymethyl groups as substituents) and in which thehydroxymethyl group or groups is or are in the positions 0 and/or p tothe phenolic hydroxyl' or hydroxyls. A

If desired, the tertiary amine salt may be made in situ, as, forexample, by passing hydrochloric acid gas into a mixture of the tertiaryamine and the substituted phenol or into a solution or suspension ofthese compounds in' an inert solvent or diluent.

In carrying the invention into practical efiect the reactants are heatedtogether, usually in such proportions that one equivalent of the aminederivative is taken for each carbinol group present in the substitutedphenol. For example, one molecular proportion of 'p-cresol dialcohol istreated with 2 molecular proportions of pyridine However, larger orsmaller proportions of the amine derivative may likewise be used.

Combination may be facilitated, in some cases, by carrying out thereaction under reduced pressure. I

If desired, the reaction may be carried out in the presence of solventsor diluents. For instance, it is advantageous in some cases to start thereaction using toluene as a solvent or diluent and at a later stage todistil 03 some or all of the toluene; this forms an azeotropic mixturewith the water which is liberated in the course of the reaction and thusaids in its removal and facili tates the completion of the reaction.

vThe substituted phenols which are used as starting materials mayconveniently be made by causing formaldehyde to react with a suitablephenol in the presence of an alkaline condensing 1 weight, illustratebut do not limit the invention.

' l'zample 1 Dry hydrochloric acid gas is passed into acooled mixture of88 parts of p-cresol dialcohol, 84 parts of pyridine and 800 partsoi'dry toluene until the weight' of the mixture has'increased .by-fparts. The mixture is then stirred and heated to 95 C. for 2 hours. Thetoluene is distilled ofl under reduced pressure and the residue isheated for 5 hours at 95 C. under 15 mm. pressure. On cooling, a hardyellowcake is obtained which is broken up and recrystallised fromethanol. There are thus obtained 130 parts of a white 0178- tallinesubstance which is very soluble in cold 15 water and has M. P. 279-281C. The product gives analyses corresponding to the formula on 01 cm I IH: I 9| Example 2 42 parts of p-tert-butylphenol dialcohol, 46 parts oi.pyridine hydrochloride and 150 parts of toluene are "stirred and heatedat 95 C. for 2 hours. The toluene is then distilled oil. under reducedpressure and the residue is heated for 8 hours at 95 C. under mm.pressure. On cooling a solid is obtained which .is recrystallised fromethanol to give a white powder which has M. P. 262' C. and isexceedingly soluble in-water.

The product gives analyses corresponding to the ture containing '19parts of pyridine and 87 parts of toluene until the weight of themixture has increased by as parts. Mpartsoi o-cresol s 1- alcohol arethen added, and the mixture is stirred andheated at 100 C. for 21mm. Thetolueneis distilled-oi! under reduced pressure and the residue heatedin. vacuo at 95' C. for 6 hours. A yellow resinous mass is obtainedwhich is dissolved in methanol, and a suiiiciency *of acetone is addedto the methanol solution to.

cause crystallisation. .Awhile crystalline mass is obtained, which isfiltered oil, washed with acetone and dried. -The-produ'ce is completelysoluble in cold waterahd has 1!. P. 79' 0.. but is not easilypurified-by Conver- 15 sion to the picrate gives a product is. P. 17H

' Dry hydrochloric acid gas is passed into a mix- C. which givesanalyses corresponding to the formula Nor-Q0 1k 4 N 'Os l I i Example 4.

168' .parts oi p'-cresol dialcohol, 259 parts of a-IJICOHIIGhydrochloride are addedto 870 parts of toluene and the mixture is heatedat 95' C. for 2 hours. The toluene is distilled oil under reducedpressure and the residue heated in vacuo at 95 C. for 16 hours. The soobtained pale yellow syrup is dissolved in water, allowed to stand andthe white, water-soluble, crystalline mass which deposits iscollected.The product has no definite M. P. (decomp. 225 C.) and gives analysescorresponding to formula 0H Cl CH: CHI

when the procedure of this example is re-' peated, using pyridinenitrate instead oi a-picoline hydrochloride, a dark yellowviscous massis obtained, which is soluble in water, formins a clear brown solution,which does not deposit a crystalline solid on standing.

Immple s 168 parts of p-cresol dialcohol and 502 parts orpyridine-p-toluene sulphonate are mixed and heated at 110 C. ior'2hours. and then at 95 C. in vacuo for 16 hours, the water iormedduringthe. reaction distils away rapidly and, after cooling, a pale yellowviscoussyrup is obtained.

The syrup dissolves easily in cold water, torming a slightly opalescentsolution. It has the probable formula trample 6 33 parts 0! p-cresoldialcohol are dissolved in 100 parts of pyridine and sulphur dioxide ispassed into the solution heated at 80' C. until -a reaction product isobtained which is completely soluble in water. Acetone is added to theP!- ridine solution and the product is precipitated water-soluble,viscous syrup.

as a brown, rum us the following,

42 parts of pyridine are dissolvedin was.

of toluene, dry hydrochloric acid gas is passed in the solutioniuntil anincrease in weight ,of 18,partsisobtained.44partsotp'-c'resol dialcoholare added and the mixture stirred at a temperature of C. for 2 hours.The toluene is distilled oil at a temperature of 140 C.,'

mass is obtained which is crystallised from ethanol giving a productidentical scribed in Example 1.

Example 8 149 parts of a carbinol prepared from technical dodecylphenol,are stirred together with 107 parts of pyridine hydrochloride and 150parts of toluene at 95 C. for 1 hour, whereby a clear solution isobtained. The toluene is then distilled ofi under reduced pressure andthe residue is heated for 8 hours at 95 C. under a pressure of 15 mm.There is thus obtained a brown viscous oil which is readily andcompletely soluble in water. It has the probable formula N\ 61:13:: N\ Il i l l v in which the 0121- and the two CH28 occupy positions 0- andpto the OH group.

The carbinol used in this example may be pre pared as follows. 131 partsoi technical dodecyL phenol are stirred into 100 parts oi watercontaining 25 parts of caustic soda and 100 parts of a 37% aqueoussolution of formaldehyde are then added. The mixture is cooled bysurrounding the container with a vessel of said water and stirred for 22hours. Both the dodecylphenol and the reaction product are incompietelysoluble in the reaction medium so that the liquid has the form of anemulsion. Saturated brine is with that dethen added to cause the oil tocollect together.

The liquid is allowed to separate into two layers and the aqueous layeris rejected. The oily iiquld is washed by repeated shaking saturatedbrine andis then neutralized by shaking with a sumcienoy oi 20% aqueousacetic acid. The emulsion so obtained is shaken with toluene and thetoluene solution of the oil is separated oil. This solution is wellwashed withwa r and dried over anhydrous magnesium suiphate.

The toluene is then distilled ofi, whereby the car binol is obtained asa brown oil.

Erample 9 156 parts of a carbinol prepared from technicaloctadecylphenol, 88.5 parts of pyridine hydra chloride and 150 parts oftoluene are stirred to gether at 95 C. for 2 hours whereby a clearsolution is obtained. The toluene is then distilled ofi under reducedpressure and the residue is heated for 6 hours at 95 C. under a pressureof 15 mm. There is thus obtained a brown, viscous oil which is readilysoluble in water. It has the probable formula in which the Cl8H37 andthe two CH: occupy positions oand pto the OH group.

, l 7 Q 3 The carbinol used in this example may. conveniently beprepared as follows. 138 parts of technical octadecylphenol are mixedwith, a l' solution of 20 parts oi caustic soda in parts of water and 80parts of a 37% aqueous solution of formaldehyde are then added. Themixture is cooled (by surroundingthe containing vessel with a bath ofcold water) and stirred at room temperature Ior 24 hours whereby anemulsion is formed. Saturated brine is then added to break the emulsionand the liquid is allowed to separate into two layers. The oily layer isremoved, neutralised by shaking with 20% aqueous acetic acid and againseparated off. It is then dissolved in toluene and the solution iswashed by shaking with a further quantity of brine. The toluene solutionof the oil is separated ofi and dried over anhydrous magnesium sulphate.The toluene is then distilled ofi under reduced pressure, whereby thecarbinol is obtained as a brown oil.

Example 1c probable formula I Cl on one 01 i I v The dialcohol used inthis example may be conveniently prepared as follows: 43 parts of pchlorophenol are dissolved in 66 parts of water containing 17.5 parts ofsodium hydroxide and 67.5 parts of a 37% aqueous solution offormaldehyde are added. The mixture is stirred-at room temperature for48 hours. Crystals separate out "and are filtered on. They are thendissolved in 700 parts of water and the solution is neutralised by, theaddition of a 20% aqueous solution of acetic acid. p-Chlorophenoldialcohoi is precipitated in the form of a crystalline mass. This isfiltered off, w mhed with brine and dried at 30 C. It then has M. P.158-159 C.

Exami ie 2E 35 parts of diphenylolpropane tetraalcohol (which may beprepared by condensing diphenylolpropane with formaldehyde in thepresence of caustic soda) and 47 parts of pyridine hydrochloride aremixed with 300'parts of toluene and heated to 90 C. for 2 hours. Thetoluene is then distilled ofi' under reduced pressure at 90 C. and theresidue is heated for 18 hours at 951?' C.-under 15mm. pressure. Thereis thus obtained a brittle yellow resinous solid which issoluble inwater and is believed to be the quaternary salt.

. Example 12 I a .55 parts of methylolstearamidoniethylphenol (iii(prepared by treating stearamidomethylphenol with paraformaldehyde'andpotassium carbonate in the presence of benzene) are dissolved in 900parts of toluene and 28.5 parts of pyridine hydrochloride are added. Themixture isstirred at 95 C. for 2 hours, the solvent removed bydistillation in vacuo at C. and the residue heated at a temperature of0., invacuo for 6 hours. There is thus obtained a waxy solid whichdissolves in water forming a faintly opalescent solution, which foams onshaking. It has the probable formula Example 13 38 parts ofp-chlorophenol dialcohol, 51.2 parts of pyridine sulphite and 45 partsof toluene are heated at 95 C. for 2 hours, the toluene is removedbydistillation in vacuo, and the mixture maintained at C. for 24 hours.There is thus obtained a brown, viscous mass, which is readily solublein water.

The water-soluble compounds obtained according to the process of theinvention are believed to be quaternary ammonium salts, the structure ofwhich is illustrated by the following equation which represents theformation of a typical salt, 4-methy1-2 6- (dimethyl'idopyridiniumchloride) phenol, from p-cresol dialcohol and pyridine hydrochloride I uno H Cl noon cmon +2 or 0H on, 01 s l W +2310 l, \J a As substitutedphenols suitable to be used for the process of the present inventionthere may be mentioned, for example, o-ihydroxybenzyl al- CHI .cohol.p-cresol, dialcohol (2 hydroiw-3-hydroxy- -methyl-5-methylphenylcarbinol), o-cresol dialcohol (2-hydroxy-3- methyl 5-hydrozymethyiphenolcarhiml), p-tert-butylphenol dialcohol(2-hydroxy-3-hydroxymethyl-5-tert-butylphenyl carbinol) dodecylphenol'carbinol, octadecylphenol carblnol, steeramidomwhylphenol carbinoi,p-chlomphenol dialcohol (2-hydroxy-3-hydmxymethyl 5 -chlorophenylcarbinol), diphenylolmethane tetraalcohol (4:4'-dihydroxy-3:5:3':5'-

. tetrahydroxymethyldiphenylmethane) di-o-cres-(3:8'-dimethyl-4:4'-diylolmethane dialcohol hydrow 5:5 dhydmxymethyldiphenyimethone), diphenylolpropane tetinalcohol di-ocresylolpropanediaicohol.

As suitable tertiary aminesalts there may be mentioned, for example. thehalides, sulphites. nitrates; m-nitmbenzene siflphonatesor p-toluenesulphonutcs of pyridine, a C-alkylpyridine or quinoline and alsoaddition compounds of-these tertiary'amines with inorganic acidanhydndes.

wherein it is anionic arias for example, sulphur dioxide or sulphurtrloxide. As particularly suitable tertiary amine salts. there may bementioned the hydrochlorides of pyridine and a-picol'ine.

This invention is a valuable advance in the art as it discloses a simplemethod of making useful assistants for dyeing cellulosic fibres. Thisprocess for obtaining luble compounds shows advantage over the known pin that interaction of a phenol with formaldehyde,

in the presence of acid, is avoided and the undesirable formation ofphenol-formaldehyde resins is thereby minimised or completely prevented.

Furthermore, this method enables one to produce a series of novelquaternary compounds, characterized by having two methylene-ammoniumradicals attached to each phenol radical.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

We claim:

1. A process for the manufacture of water-soluble compounds, whichcompri-sesinteracting a phenol having at least one hydroxyme thylsubstituent in ortho position, with a compound selected from the groupconsisting of the addition products of acids and acid anhydrides withpyridine, the C-alkyl pyridines and quinoline.

2. A process for the manufacture of water-soluble compounds, whichcomprises interacting a phenol having at least one hydroxymethylsubstituent in ortho position and at least one further substituentselected from the group consisting of halogen, acylamido,acylamidomethyl, alkyl,

aralkyl and hydroxyaralkyl, with a compound selected trom the groupconsisting of the addition products of acids and acid anhydrides withpyridine, the C-alkyl pyridines and quinoline.

3. A process for the manufacture of watersolublecompounds, whichcomprises interacting a di hydroxymethyl phenol with a compound selectedfrom the group consisting of the addition products of acisk and acidanhydrides with pyridine, the C-alkyl pyridines and quinoline.

4. A process for the manufacture of water- I soluble compounds, whichcomprises interacting an ortho, ortho'-di(hydroxymethyl) -phenol with acompound selected from the group consisting of the addition products ofacids and acid anhydrides with pyridine, the C-alkyl pyridines andquinoline.

5. Quaternary salts of the general formula HOAr- '(CHsNtert-x )a,wherein Ar is an aryl radical of the benzene series, Ntert stands forthe nucleus of a cyclic tertiary base selected from the group consistingof pyridine, the C-albl pyridines and quin0line,.while x stands for ananionic radical, and wherein the radicals (CH:- Ntert.-x) occupypositions in the Ar nucleus other than meta to the OH group.

6. A quaternary salt of-the general formula (ill pyridines andquinoline, while Q, Y, Z stand for substituents selected from the groupconsisting of hydrogen, halogen, acylamido, acylamidomethyl, alkyl,aralkyl and hydroxy-aralkyl.

7. A quaternary salt of the general formula.

aralkyl.

8. A quaternary salt of the general formula on fiihjcp (minim whereinAlk stands for an alkyl radical having not less than 8 carbon atomsinits structure.

9. A process for producing a quaternary ammonium compound, whichcomprises reacting with formaldehyde and alkali upon a phenol of thegeneral formula wherein R is an alkyl radical having not less than 8carbon atoms, to produce an intermediate hydroxy'-phenyl-carhinolcompound of the general iormula omen).

wherein R has the same significance as above,

while a: is an integer less than 3, and then condensing saidintermediate hydroxy-phenyl-carbinol compound with a compound selectedfrom the group consisting of the addition products of acids and acidanhydrides with pyridine, the I -alkyl-pyridines or quinoline.

REGINALD JOHN REYNOLDS. 25

ERIC EVERARD WALKER.

